Method for manufacturing pre-adhesive materials and laminates for substrate processing

Abstract

This invention relates to a pre-adhesive material for substrate processing, used for pre-adheding a substrate to be processed on the back side to a support. The pre-adhesive material is characterized by containing, relative to 10 parts by mass and 100 parts by mass, a polymer containing siloxane bonds with a weight average molecular weight of 3,000 to 700,000 as determined by GPC. The pre-adhesive material has a first pre-adhesive layer and a second pre-adhesive layer different from the first pre-adhesive layer. At least one of the first and second pre-adhesive layers has a minimum shear viscosity of 1 Pa·s to 10,000 Pa·s in the range of 130°C to 250°C. This provides a pre-adhesive material for substrate processing that facilitates pre-adhesion and peeling between the substrate and the support, provides a fast pre-adhesive layer formation step, exhibits excellent dimensional stability and thermal process resistance, and improves the productivity of thin substrates. A method for manufacturing a laminate using the pre-adhesive material is also provided.

Description

[Technical Field]

[0001] The present invention relates to a pre-adhesive material for substrate processing and a method for manufacturing a laminate using the pre-adhesive material for substrate processing. [Previous Technology]

[0002] 3D semiconductor mounting is essential for achieving higher density and larger capacity. 3D mounting technology involves thinning a semiconductor wafer and then using through-silicon vias (TSVs) to simultaneously fabricate multiple layers of semiconductors. To achieve this, the substrate containing the semiconductor circuitry needs to be thinned by grinding the non-circuit-forming surface (also known as the "back side"), and then electrodes including the TSVs are formed on the back side.

[0003] In the past, during the back-side grinding process of silicon substrates, protective tape was applied to the opposite side of the grinding surface to prevent substrate damage during grinding. However, this tape uses an organic resin film to support the substrate, which is flexible, but on the other hand, its strength or heat resistance is insufficient, making it unsuitable for the TSV formation process or the wiring layer formation process on the back side.

[0004] Therefore, there are proposals for systems that bond semiconductor substrates to supports such as silicon and glass via an adhesive layer, and that can sufficiently withstand back-side grinding, TSV, or back-side electrode formation steps. The adhesive layer used to bond the substrate to the support is crucial in this case. It needs to bond the substrate to the support without gaps, possess sufficient durability to withstand subsequent steps, and ultimately allow for easy peeling of the thin substrate from the support. Thus, due to the final peeling, this adhesive layer is referred to in this specification as a pre-adhesive layer (or pre-adhesive material layer).

[0005] Currently, as well-known pre-bonded layers and their peeling methods, there are proposals for techniques such as irradiating an adhesive containing a light-absorbing substance with high-intensity light to decompose the adhesive layer and peel it off from the support (Patent Document 1), and techniques such as using a thermally fusible hydrocarbon compound on the adhesive and bonding and peeling in a heated and molten state (Patent Document 2). The former technique requires expensive equipment such as lasers and has problems such as longer processing time per substrate. The latter technique is simple because it is controlled only by heating, but on the other hand, its application range is narrow due to insufficient thermal stability at temperatures exceeding 200°C. Furthermore, although these pre-bonded layers are not suitable for uniform film thickness formation on substrates with high gradients and for complete bonding to the support, they cannot peel the substrate and support in subsequent steps, often causing damage to the substrate. [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2004-64040 [Patent Document 2] Japanese Invention Patent No. 6059631 [Summary of the Invention]

[0007] [The problem that the invention aims to solve]

[0008] This invention was made in view of the above-mentioned problems, and its object is to provide a pre-bonding material for substrate processing that facilitates pre-bonding and peeling of the substrate and support, is rapid in the pre-bonding material layer formation step for the substrate or support, exhibits excellent dimensional stability, excellent resistance to thermal processes such as CVD (chemical vapor deposition), and is easy to peel off, thereby improving the productivity of laminates; and a method for manufacturing laminates using the pre-bonding material for substrate processing. [Means for Solving the Problems]

[0009] In order to solve the above-mentioned problems, the present invention provides a pre-adhesive material for substrate processing, which is used to pre-adhere a substrate to be processed on the back side to a support. The pre-adhesive material is characterized in that: relative to 100 parts by mass, the pre-adhesive material contains 10 to 100 parts by mass of a polymer containing siloxane bonds with a weight average molecular weight of 3,000 to 700,000 as determined by GPC; the pre-adhesive material has a first pre-adhesive layer and a second pre-adhesive layer different from the first pre-adhesive layer; any one or both (at least one) of the first pre-adhesive layer and the second pre-adhesive layer has a minimum shear viscosity of 1 Pa·s to 10,000 Pa·s in the range of 130°C to 250°C.

[0010] If the substrate processing pre-bonding material of the present invention is such, the pre-bonding of the substrate-support is easy, the dimensional stability is excellent, the pre-bonding material layer formation speed is high, the step suitability for TSV formation and back-side wiring of the substrate is high, and the resistance to thermal processes such as CVD is also good, and peeling is easy, which can improve the productivity of thin substrates.

[0011] At this time, the aforementioned first pre-adhesive layer may be composed of thermoplastic resin.

[0012] If such a pre-bonding material is used for substrate processing, the processed substrate can be easily cleaned, thus further improving the productivity of thin substrates.

[0013] At this time, the aforementioned polymer containing siloxane bonds may have repeating units as shown in the following general formula (1). [In the formula, R1 to R4 represent monovalent hydrocarbon groups with 1 to 8 carbon atoms that may be the same or different; m is an integer from 1 to 100, B is a positive number, and A is 0 or a positive number; however, A+B=1; X is a divalent organic group as shown in the following general formula (2); (in the formula, Z is a divalent organic group selected from any of them, N is 0 or 1; R5 and R6 are each alkyl or alkoxy groups with 1 to 4 carbon atoms that may be the same or different from each other; k is any one of 0, 1, or 2)].

[0014] Furthermore, the aforementioned polymers containing siloxane bonds may also have repeating units as shown in the following general formula (3). [In the formula, R7 to R10 represent monovalent hydrocarbon groups with 1 to 8 carbon atoms that may be the same or different; n is an integer from 1 to 100, D is a positive number, and C is 0 or a positive number; however, C+D=1; furthermore, Y is a divalent organic group as shown in the following general formula (4); (in the formula, V is a divalent organic group selected from any of them, p is 0 or 1; furthermore, R11 and R12 are each alkyl or alkoxy groups with 1 to 4 carbon atoms that may be the same or different from each other; h is any one of 0, 1, or 2)].

[0015] Furthermore, the aforementioned polymer containing siloxane bonds may also contain the following: (p1) an organopolysiloxane having an alkenyl group in the molecule, (p2) an organohydrogen polysiloxane containing two or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule: the molar ratio of the Si-H groups in the (p2) component to the alkenyl group in the aforementioned (p1) component is 0.3 to 15, and (p3) a platinum-based catalyst.

[0016] If the pre-adhesive material for substrate processing of the present invention is such, its heat resistance is even better and more suitable.

[0017] Furthermore, the present invention also provides a method for manufacturing a laminate, which is a method for manufacturing a laminate in which a substrate and a support are bonded together through a pre-adhesive material, characterized by comprising the following steps (a) to (d): (a) forming a pre-adhesive layer on the bonding surface of either or both of the substrate and the support using the aforementioned pre-adhesive material for substrate processing; (b) preheating either or both of the aforementioned substrate and the aforementioned support to a temperature of 30°C to 100°C; (c) bringing the aforementioned substrate and the aforementioned support into contact under reduced pressure through the aforementioned pre-adhesive material, and applying pressure at a pressure of 1 MPa or less; (d) maintaining the pressurized state and heating the substrate temperature to a temperature of 130°C to 250°C.

[0018] With such a method of manufacturing the laminate, when a substrate with an uneven surface is bonded to a support through a pre-adhesive, the laminate can be manufactured without gaps. [Effects of the Invention]

[0019] As described above, if it is the pre-adhesive material for substrate processing of the present invention, the pre-adhesion between the substrate and the support is easy, the pre-adhesive layer formation step for the substrate or support is fast, and it has excellent dimensional stability, excellent resistance to thermal processes such as CVD (chemical vapor deposition), and is easy to peel off, which can improve the productivity of the laminate. Furthermore, when separating the substrate and the support after pre-adhesion, since separation is possible on the surface or in the pre-adhesive layer, thin substrates with through-electrode structures or bump connection structures can be easily manufactured. Furthermore, even for substrates with step differences, an adhesive layer with high film thickness uniformity can be formed. Due to this film thickness uniformity, uniform laminates (thin substrates, etc.) with a thickness of less than 50 μm can be easily obtained. Furthermore, after the laminate is manufactured, since the substrate can be easily peeled off from the support, for example at room temperature, it is easy to manufacture easily crackable laminates such as thin substrates.

Implementation Method

[0020] [Form of Invention]

[0021] As described above, a pre-adhesive for substrate processing is required, which is easy to pre-adhere, has a fast adhesive layer formation speed for substrates or supports, excellent dimensional stability, excellent resistance to substrate thermal processes such as CVD, and is easy to peel off, thereby improving the productivity of thin substrates.

[0022] The inventors have diligently conducted research to achieve the above-mentioned objectives and have discovered that by using a pre-bonding material for substrate processing, a thin substrate having a through-electrode structure or a bump connection structure can be easily manufactured, thus completing the present invention. This pre-bonding material for substrate processing is used to pre-bond a substrate to be processed on the back side to a support. Its characteristics are: the aforementioned pre-bonding material contains, relative to its total mass, 10 to 100 parts by mass of a polymer containing siloxane bonds, with a weight average molecular weight of 3,000 to 700,000 as determined by gel permeation chromatography (GPC); the aforementioned pre-bonding material has a first pre-bonding layer and a second pre-bonding layer different from the aforementioned first pre-bonding layer. The minimum shear viscosity of at least one of the aforementioned first pre-bonded material layer and the aforementioned second pre-bonded material layer is 1 Pa·s to 10,000 Pa·s in the range of 130°C to 250°C, preferably 5 Pa·s to 8,000 Pa·s.

[0023] The present invention will be described in detail below, but the invention is not limited thereto. Furthermore, in this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene conversion values ​​obtained using a calibration curve of standard polystyrene via gel permeation chromatography (GPC).

[0024] [Pre-bonding material for substrate processing] The pre-bonding material for substrate processing of the present invention is used to pre-bond a substrate to be processed on the back side to a support, characterized in that: relative to its total mass of 100 parts, it contains 10 to 100 parts by mass of a polymer containing siloxane bonds, which has a weight average molecular weight of 3,000 to 700,000 as determined by GPC, the aforementioned pre-bonding material has a first pre-bonding material layer and a second pre-bonding material layer different from the aforementioned first pre-bonding material layer, and any one or both of the aforementioned first pre-bonding material layer and the aforementioned second pre-bonding material layer (i.e., at least one layer) has a minimum shear viscosity of 1 Pa·s to 10,000 Pa·s in the range of 130°C to 250°C.

[0025] As shown in FIG. 1, the pre-adhesive material for substrate processing of the present invention has (A) a first pre-adhesive layer and (B) a second pre-adhesive layer different from the aforementioned first pre-adhesive layer, forming a substrate 1 to be processed on the back side, a support 3 supporting the substrate 1 during processing of the substrate 1, and a pre-adhesive layer 2 between the substrate 1 and the support 3. This pre-adhesive layer 2 is composed of a two-layer structure of (A) the first pre-adhesive layer and (B) the second pre-adhesive layer. In FIG. 1, the first pre-adhesive layer is peelably bonded to the surface of the substrate 1, and the second pre-adhesive layer is peelably bonded to the surface of the support 3. However, conversely, the first pre-adhesive layer can be peelably bonded to the surface of the support 3, and the second pre-adhesive layer can be peelably bonded to the surface of the substrate 1.

[0026] Furthermore, a necessary condition for the pre-adhesive material for substrate processing of the present invention is that, relative to 100 parts by mass and less than 100 parts by mass of the aforementioned polymer containing siloxane bonds, the minimum shear viscosity of either or both of the first pre-adhesive layer and the second pre-adhesive layer is within the aforementioned range. If the pre-adhesive material for substrate processing of the present invention is such, then since the adhesion between the substrate and the pre-adhesive layer, between the support and the pre-adhesive layer, and between the first pre-adhesive layer and the second pre-adhesive layer becomes appropriate, separation can be achieved on the surface or within the pre-adhesive layer when separating the substrate and the support after pre-adhesion. Here, the so-called surface of the pre-adhesive layer refers to the surface of the pre-adhesive layer that can be peelably bonded to the substrate or the support (the bonding surface between the substrate or the support and the pre-adhesive layer), and the term "within the pre-adhesive layer" is not particularly limited to the interior of the pre-adhesive layer, but can be, for example, the bonding surface between the first pre-adhesive layer and the second pre-adhesive layer. Furthermore, the shear viscosity in this invention is determined by viscosity measurement within a temperature range of 130°C to 250°C using the method described in JIS K 7244. The minimum shear viscosity of each layer is the minimum shear viscosity within the aforementioned temperature range.

[0027] [Laminated Structure] As shown in FIG1, the laminated system of the present invention comprises a substrate 1 to be processed on the back side, a support 3 for supporting the substrate 1 during processing of the substrate 1, and a pre-adhesive layer 2 between the substrate 1 and the support 3. The pre-adhesive layer 2 is as described above, consisting of a two-layer structure of (A) a first pre-adhesive layer and (B) a second pre-adhesive layer, either of which may be on the substrate side.

[0028] [Pre-adhesive Layer] The pre-adhesive layer is composed of a two-layer structure consisting of a first pre-adhesive layer and a second pre-adhesive layer, which is different from the first pre-adhesive layer. This pre-adhesive layer contains 10 to 100 parts by mass of the aforementioned polymer containing siloxane bonds relative to its total mass of 100 parts. At least one of the aforementioned first and second pre-adhesive layers has a minimum shear viscosity of 1 Pa·s to 10,000 Pa·s within the range of 130°C to 250°C. By using a shear viscosity within this range, the pre-adhesive material can be well embedded in a substrate with a stepped surface. There are no particular limitations on the pre-adhesive layer as long as it meets the above conditions. If the content of the aforementioned polymer containing siloxane bonds is less than 10 parts by mass relative to 100 parts by mass of the total pre-bonding material, it is not considered a pre-bonding material for substrate processing that is easy to pre-bond and peel off, has a fast pre-bonding layer formation speed for the substrate or support, excellent dimensional stability, and excellent heat process resistance. Furthermore, if the first pre-bonding layer and the second pre-bonding layer are identical, the peeling performance is poor; if the minimum shear viscosity of both the first and second pre-bonding layers is less than 1 Pa·s or exceeds 10,000 Pa·s in the range of 130°C to 250°C, the adhesion is poor.

[0029] The materials (resins) constituting each layer can be thermoplastic resins or thermosetting resins, as long as they meet the above conditions. The materials constituting each layer will be described below.

[0030] <Thermoplastic Resin> In the pre-adhesive layer, the first pre-adhesive layer (A) may be composed of a thermoplastic resin. From the perspective of applicability to substrates with stepped surfaces, it is preferable to use a thermoplastic resin with good embedding properties as the material for forming the first pre-adhesive layer (A). In particular, it is preferable to use a thermoplastic resin that does not have an organopolysiloxane glass transition temperature of about -80 to 150°C, such as olefin-based thermoplastic elastomers, polybutadiene-based thermoplastic elastomers, styrene-based thermoplastic elastomers, styrene-butadiene-based thermoplastic elastomers, styrene-polyolefin-based thermoplastic elastomers, etc., and hydrogenated polystyrene-based elastomers with excellent heat resistance are particularly preferred.

[0031] Commercially available thermoplastic resins can be used, specifically including Taftec (Asahi Kasei Chemicals), Espolex SB series (Sumitomo Chemicals), Lavalon (Mitsubishi Chemical), Septon (KURARAY), and DYNARON (JSR). Also, cyclic olefin polymers represented by Zeonex (Japan ZEON) and cyclic olefin copolymers represented by TOPA・S (Japan POLYPLASTIC) can be cited.

[0032] As described above, the thermoplastic resin used as the first pre-adhesive layer (A) is preferably a thermoplastic elastomer. Alternatively, two or more resins may be used together.

[0033] If this is the case, after the laminate (thin substrate, etc.) is manufactured, the pre-bonding material can be more easily peeled off or washed away from the substrate, so it is easier to handle fragile thin substrates.

[0034] The above-mentioned thermoplastic resin (composition) is soluble in a solvent to form a pre-adhesive solution for the formation of a pre-adhesive layer. Examples of solvents include hydrocarbon solvents, with nonane, p-menthane, pinene, isooctane, and mesitylene being preferred. However, from the perspective of coatability, nonane, p-menthane, isooctane, and mesitylene are more preferred. Furthermore, filtration may be performed as needed. Subsequently, it is preferable to use a forward roller coater, reverse roller coater, corner roller coater, die coater, lip coater, gravure coater, dip coater, air knife coater, capillary coater, R&R coater, doctor blade coater, bar coater, applicator, extrusion molding machine, etc., for example, to coat the substrate (release substrate). Subsequently, the solvent is removed from the support coated with the pre-adhesive solution within the line to form a pre-adhesive layer.

[0035] At this time, there is no limitation on the film thickness formed, but it is desirable to form a resin film (pre-adhesive layer) on the support, preferably with a film thickness of 0.5 to 80 μm, and more preferably 0.5 to 50 μm. Furthermore, in this thermoplastic resin, antioxidants may be added to improve its heat resistance, or surfactants may be added to improve coatability. Specific examples of antioxidants include di-tert-butylphenol. Examples of surfactants include fluorinated polysiloxane surfactants such as X-70-1102 (manufactured by Shin-Etsu Chemical Co., Ltd.). Moreover, while the above describes an example of forming the first pre-adhesive layer on the support, it can also be formed on the substrate to be processed on the back side, or on top of the second pre-adhesive layer. Furthermore, the lamination order of the first and second pre-adhesive layers can also be reversed.

[0036] <Thermosetting Resin> The pre-adhesive layers (first pre-adhesive layer and second pre-adhesive layer) may be composed of a thermosetting resin. Preferably, the thermosetting resin is a thermosetting resin with a polymer containing siloxane bonds as the main component. In this invention, when the pre-adhesive layer contains 10 to 100 parts by mass of a polymer containing siloxane bonds with a weight average molecular weight of 3,000 to 700,000 as determined by GPC, relative to 100 parts by total mass, the aforementioned polymer containing siloxane bonds is not particularly limited, but a polymer composed mainly of a thermosetting siloxane-modified polymer as shown in the following general formula (1) and / or (3), or a polymer composed mainly of an addition-curing siloxane polymer, may be used.

[0037] Furthermore, in the pre-adhesive layer, the polymer shown in the following general formula (1) and the polymer shown in the following general formula (3) can be used together. The preferred ratio (mass ratio) is (1):(3)=0.1:99.9~99.9:0.1, and more preferably (1):(3)=1:99~99:1.

[0038] Polymer of general formula (1) (phenolic silicate polymer): A polymer containing silicate bonds having a polystyrene equivalent weight average molecular weight of 3,000 to 500,000, preferably 10,000 to 100,000, as determined by gel permeation chromatography (GPC), having repeating units as shown in the following general formula (1). [Where R1 to R4 represent monovalent hydrocarbon groups with 1 to 8 carbon atoms that may be the same or different; m is an integer from 1 to 100, B is a positive number, A is 0 or a positive number; X is a divalent organic group as shown in the following general formula (2); A+B=1. Also, preferably A is 0 to 0.9, B is 0.1 to 1, and when A is greater than 0, preferably A is 0.1 to 0.7, B is 0.3 to 0.9.] (In the formula, Z is a divalent organic group selected from any of them, N is 0 or 1; and R5 and R6 are each alkyl or alkoxy groups with 1 to 4 carbon atoms, which may be the same or different from each other; k is any one of 0, 1, or 2)).

[0039] At this time, specific examples of R1 to R4 can be methyl, ethyl, phenyl, etc., where m is an integer from 1 to 100, preferably from 3 to 60, and more preferably from 8 to 40. Also, B / A is greater than 0 and less than 20, especially from 0.5 to 5.

[0040] Polymer of general formula (3) (epoxy-modified siloxane polymer): A polymer containing siloxane bonds with a polystyrene equivalent weight average molecular weight of 3,000 to 500,000 as determined by GPC, having repeating units as shown in the following general formula (3). [Where R7 to R10 represent monovalent hydrocarbon groups with 1 to 8 carbon atoms that may be the same or different; n is an integer from 1 to 100, D is a positive number, and C is 0 or a positive number. Furthermore, Y is a divalent organic group as shown in the following general formula (4). C+D=1. Furthermore, it is preferred that C is 0 to 0.9, D is 0.1 to 1, and when C is greater than 0, it is preferred that C is 0.1 to 0.7, and D is 0.3 to 0.9.] (In the formula, V is a divalent organic group selected from any of them, and p is 0 or 1. Also, R11 and R12 are each alkyl or alkoxy groups with 1 to 4 carbon atoms, which may be the same or different from each other. h is any of 0, 1, or 2).

[0041] At this time, as specific examples of R7 to R10, the same examples as those exemplified by R1 to R4 in the above general formula (1) can be given. Also, n is an integer from 1 to 100, preferably from 3 to 60, and more preferably from 8 to 40. Also, D / C is greater than 0 and less than 20, especially from 0.5 to 5.

[0042] The thermosetting composition with the thermosetting silicone modified polymer of the above general formula (1) and / or (3) as the main component is for thermosetting purposes. In the case of the phenolic silicone polymer of general formula (1), it may contain one or more crosslinking agents selected from amino condensates modified by formalin or formalin-alcohol, melamine resin, urea resin, phenolic compounds having an average of more than 2 hydroxymethyl or alkoxyhydroxymethyl (alkoxymethyl) groups in 1 molecule and epoxy compounds having an average of more than 2 epoxy groups in 1 molecule.

[0043] Here, examples of amine condensates, melamine resins, and urea resins modified by formalin or formalin-alcohol include the following. For example, the melamine resin (condensate) modified by formalin or formalin-alcohol can be a partial condensate of alkoxymethyl melamine such as hexamethoxymethyl melamine, or it can be obtained by addition condensation polymerization of modified melamine monomers (e.g., trimethoxymethyl monomethyl melamine) or polymers thereof (e.g., oligomers such as dimers and trimers) with formaldehyde according to well-known methods until the desired molecular weight is achieved. Furthermore, one or more of these can be used.

[0044] Furthermore, the preparation of urea resins (condensates) modified by formalin or formalin-alcohol can be carried out, for example, by modifying the urea condensate of the desired molecular weight with formalin through hydroxymethylation, or by further modifying it with an alcohol through alkoxylation, according to well-known methods. Specific examples of urea resins modified by formalin or formalin-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates. Moreover, one or more of these can be used.

[0045] Furthermore, examples of phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl (alkoxymethyl) groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A. Moreover, such phenolic compounds can be used as one type or in mixtures of two or more.

[0046] On the other hand, in the case of epoxy-modified silicate polymer of general formula (3), one or more of the following may be contained as a crosslinking agent: an epoxy compound having an average of two or more epoxy groups in one molecule or a phenol compound having an average of two or more phenol groups in one molecule.

[0047] Here, there is no particular limitation on the epoxy compound with polyfunctional epoxy groups used in general formula (1), and it may contain polyfunctional epoxy resins with 2, 3 or more functions, such as EOCN-1020, EOCN-102S, XD-1000, NC-2000-L, EPPN-201, GAN, NC6000 or crosslinking agents as described below manufactured by Nippon Kayaku Co., Ltd.

[0048] When the thermosetting polymer is an epoxy-modified silicate polymer of the above general formula (3), specific examples of phenolic compounds having an average of 2 or more phenolic groups in one molecule as crosslinking agents can be given as m, p-series cresol phenolic resins, such as EP-6030G manufactured by Asahi Organic Materials Co., Ltd., or trifunctional phenolic compounds, such as Tris-P-PA manufactured by Honshu Chemical Co., Ltd., or tetrafunctional phenolic compounds, such as TEP-TPA manufactured by Asahi Organic Materials Co., Ltd.

[0049] The amount of crosslinking agent can be 0.1 to 50 parts by mass relative to 100 parts by mass of the thermosetting polymer of the above general formula (1) or formula (3), preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass. Two or more types can be mixed together.

[0050] Furthermore, relative to 100 parts by mass of the thermosetting polymer, it may contain 10 parts by mass or less of a curing catalyst such as an acid anhydride.

[0051] The above-mentioned thermosetting resin (composition) is soluble in a solvent and can be used as a pre-adhesive layer solution for the formation of the pre-adhesive layer. Examples of solvents include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentanone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, and γ-butyrolactone. One or more of these solvents can be used alone or in combination. Furthermore, filtration can be performed as needed.

[0052] Furthermore, to further improve heat resistance, up to 50 parts by weight of a well-known antioxidant, silica, or other similar material may be added relative to 100 parts by weight of the thermosetting polymer. Additionally, to improve coating uniformity, a surfactant may be added. Furthermore, to improve peelability, a peel enhancer may be added.

[0053] Specific examples of antioxidants that can be added to the pre-adhesive layer include hindered phenolic compounds such as tetra[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (trade name: ADK STAB AO-60).

[0054] At this time, there is no particular limitation on the film thickness formed, but it is preferably 5 to 150 μm, more preferably 10 to 120 μm. If the film thickness is 5 μm or more, it can withstand the grinding steps of substrate thinning. If it is 150 μm or less, there is no risk of resin deformation during heat treatment steps such as TSV formation, and it is more suitable for practical use.

[0055] Addition-curing silicone polymer: Furthermore, the pre-adhesive layer may be an addition-curing silicone polymer containing the following components (p1), (p2), and (p3).

[0056] (p1) Organic polysiloxane having an alkenyl group in the molecule: 100 parts by mass; (p2) Organic hydrogen polysiloxane containing two or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule: the molar ratio of the Si-H groups in the (p2) component to the alkenyl group in the aforementioned (p1) component is 0.3 to 15; (p3) Platinum-based catalyst: the effective component (mass conversion) is more than 0 parts by mass and less than 0.5 parts by mass.

[0057] The following describes each component.

[0058] [(p1) Component] (p1) Component is an organopolysiloxane containing an alkenyl group in the molecule. (p1) Component is preferably a linear or branched organopolysiloxane containing an alkenyl group with a mole percentage of alkenyl group relative to the number of Si moles in one molecule (alkenyl mole / Si mole). Particularly preferred is an organopolysiloxane containing an alkenyl group with a mole percentage of alkenyl group relative to the aforementioned number of Si moles.

[0059] Specifically, examples of such organopolysiloxanes include those shown in formulas (5) and / or (6) below. (In the formulas, R13 are each independently a monovalent hydrocarbon group without aliphatic unsaturated bonds, X1 are each independently a monovalent organic group containing an alkenyl group, and a is an integer from 0 to 3. Also, in formula (5), 2a+1 is a number in which the alkenyl content in one molecule is 0.3 to 10 mol%. In formula (6), l+2 is a number in which the alkenyl content in one molecule is 0.3 to 10 mol%. l is a positive number less than 0 or 500, and r is a positive number from 1 to 10,000).

[0060] In the above formula, R13 is preferably a monovalent hydrocarbon group with 1 to 10 carbon atoms that does not have an aliphatic unsaturated bond, such as alkyl groups like methyl, ethyl, propyl, butyl, etc.; cycloalkyl groups like cyclohexyl; aryl groups like phenyl, tolyl, etc., and especially preferably alkyl groups like methyl or phenyl.

[0061] As X1, the monovalent organic group containing an alkenyl group is preferably an organic group having 2 to 10 carbon atoms, such as alkenyl groups like vinyl, allyl, hexenyl, and octenyl; (meth)acrylylalkyl groups like acryloxypropyl, acryloxymethyl, and methacrylpropyl; (meth)acryloxyalkyl groups like acryloxypropyl, acryloxymethyl, methacryloxypropyl, and methacryloxymethyl; and monovalent hydrocarbon groups containing an alkenyl group like cyclohexeneethyl and vinyloxypropyl, with vinyl being particularly preferred in industry.

[0062] In the above general formula (5), a is an integer from 0 to 3. If a is 1 to 3, since the end of the molecular chain is blocked by the alkenyl group, the reaction can be completed in a short time through the alkenyl group at the end of the molecular chain, which has good reactivity. Furthermore, in terms of cost, a=1 is more industrially feasible. The shape of the alkenyl-containing organopolysiloxane is preferably oily or rubbery. The alkenyl-containing organopolysiloxane can be linear or branched. Also, two or more components (p1) can be used together.

[0063] Moreover, the number average molecular weight (Mn) of the above-mentioned (p1) component, as determined by GPC, is preferably 100,000 to 500,000.

[0064] [(p2) component] The (p2) component is a crosslinking agent, which is an organohydrogen polysiloxane containing two or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule. The (p2) component has at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, preferably two to 100, more preferably three to 50, and can be linear, branched or cyclic.

[0065] (p2) The viscosity of the organohydrogen polysiloxane component at 25°C is preferably 1 to 5,000 mPa·s, more preferably 5 to 500 mPa·s. This organohydrogen polysiloxane may also be a mixture of two or more types. Furthermore, the viscosity is measured using a rotational viscometer.

[0066] The (p2) component is blended in such a manner that the molar ratio (Si-H group / alkenyl group) of the Si-H group in the (p2) component to the alkenyl group in the (p1) component is 0.3 to 15, preferably 0.3 to 10, and most preferably 1 to 8. When the molar ratio of Si-H group to alkenyl group is 0.3 or higher, there is no risk of reduced crosslinking density and no risk of problems such as insufficient hardening of the adhesive layer. If it is 15 or lower, there is no risk of excessively high crosslinking density, and sufficient adhesion and tack can be obtained.

[0067] [(p3) Components] (p3) Components are platinum group catalysts (i.e., platinum group metal catalysts), for example, chloroplatinic acid, alcoholic solutions of chloroplatinic acid, reactants of chloroplatinic acid and alcohols, reactants of chloroplatinic acid and olefin compounds, reactants of chloroplatinic acid and vinyl-containing siloxanes, etc.

[0068] The amount of component (p3) added is an effective amount, and is generally 1 to 5,000 ppm (by mass) relative to the total of (p1) and (p2), preferably 5 to 2,000 ppm. If it is above 1 ppm, the hardening properties of the composition will not decrease, and the holding power will not decrease even if the crosslinking density decreases. If it is below 5,000 ppm, the usable time of the treatment solution can be increased.

[0069] The above-mentioned thermosetting silica polymer layer composition can be dissolved in a solvent to form a pre-adhesive solution for the formation of a pre-adhesive layer. As a solvent, suitable solvents include hydrocarbon solvents such as pentane, hexane, cyclohexane, isooctane, nonane, decane, p-menthane, pinene, isododecane, and limonene, or volatile low-molecular-weight silicates such as hexamethyldisiloxane or octamethyltrisiloxane. One or more of these solvents can be used alone. Furthermore, to improve heat resistance, well-known antioxidants can be added to this thermosetting silica polymer layer composition. Additionally, filtration can be performed as needed.

[0070] At this time, the film thickness formed is preferably 0.1 to 30 μm, and particularly preferably between 1.0 and 15 μm. If the film thickness is 0.1 μm or more, it is easier to peel off from the substrate or support. On the other hand, if the film thickness is 30 μm or less, it can sufficiently withstand the grinding steps when forming a thin wafer. Furthermore, in order to further improve the heat resistance in this thermosetting silicone polymer layer, up to 50 parts by mass of filler such as silicon dioxide can be added relative to 100 parts by mass of the total mixture of the thermosetting silicone polymer components (p1), (p2), and (p3).

[0071] [Method for manufacturing a laminate] The method for manufacturing a laminate of the present invention includes steps (a) to (d). [Step (a)] Step (a) is the step of forming a pre-adhesive layer on the bonding surface of either or both of the substrate and the support body using the pre-adhesive material for substrate processing of the present invention described above.

[0072] The substrate to be processed is, for example, a substrate with one side being the circuit formation surface and the other side (back side) being the non-circuit formation surface. The substrate to which this invention is applicable is typically a semiconductor substrate. Examples of such semiconductor substrates include disk-shaped wafers or square substrates. Examples of wafers include not only silicon wafers, but also germanium wafers, gallium-arsenic wafers, gallium-phosphorus wafers, gallium-arsenic-aluminum wafers, etc. The thickness of the substrate is not particularly limited, but is typically 600–800 μm, and more typically 625–775 μm.

[0073] In particular, in the manufacturing method of the multilayer (thin wafer, etc.) of the present invention, a substrate system having a step difference on the surface caused by the circuit is effective, especially a substrate system with a step difference of 10 to 80 μm, preferably 20 to 70 μm.

[0074] There are no particular limitations on the support; a silicon wafer, glass plate, quartz wafer, or other substrate can be used. In this invention, it is not necessary to irradiate the pre-adhesive layer with radiation energy lines through the support, and the support may not be light-transmitting.

[0075] The first pre-adhesive layer and the second pre-adhesive layer can each be formed as thin films on a substrate (wafer) or support, or their respective solutions can be formed on the wafer or support by spin coating, roll coating, or other methods. In this case, after spin coating, the substrate or support is pre-heat-treated at a temperature of 80–200°C, preferably 100–180°C, according to the solvent evaporation conditions, before use. The first pre-adhesive layer and the second pre-adhesive layer can both be formed on the substrate or support, or only one can be formed on either the substrate or support. Examples of methods for forming the pre-adhesive layer are given below.

[0076] [Forming Method 1] A first pre-adhesive layer is formed on a support using a solution of a first pre-adhesive layer, and then a second pre-adhesive layer is formed on the formed first pre-adhesive layer using a solution of a second pre-adhesive layer.

[0077] [Forming Method 2] A first pre-adhesive layer is formed on a support using a solution of the first pre-adhesive layer. Separately, a second pre-adhesive layer is formed on a substrate using a solution of the second pre-adhesive layer.

[0078] Furthermore, when each adhesive layer is formed by a thin film, the constituent components of the present invention can be formed on a protective film such as polyethylene or polyester, and the protective film can be peeled off for use.

[0079] Steps (b) to (d) are steps for bonding the aforementioned substrate and support. Commercially available wafer bonding devices can be used as substrate bonding apparatuses during wafer fabrication, such as EVG520IS and 850TB from EVG Corporation, and XBS300 from SUSS Corporation. The substrate and support can be arranged within the apparatus in a manner that allows them to be bonded with a pre-adhesive material. For example, in the above-described forming method 1, when forming the first pre-adhesive layer and the second pre-adhesive layer on the support, the surface of the substrate where the pre-adhesive layer is to be formed can be aligned with the surface of the support where the pre-adhesive layer is formed. Similarly, in the above-described forming method 2, when forming the first pre-adhesive layer or the second pre-adhesive layer on either the substrate or the support, the surface of the substrate where the pre-adhesive layer is formed can be aligned with the surface of the support where the pre-adhesive layer is formed, and the arrangement is within the apparatus.

[0080] [Step (b)] Step (b) is a step of preheating either or both of the substrate and the support. In this case, the heating means is built into the bonding device, and a heater is built into the plate (cavity) where the substrate and the support are mounted. Furthermore, the heater can be any well-known heating device. Either or both of the aforementioned substrate and the support are heated to a temperature of 30°C to 100°C.

[0081] [Step (c)] Step (c) is a step in which the substrate and the support are brought into contact under reduced pressure with a pressure of 1 MPa or less, separated by a pre-bonding material. For example, the substrate is uniformly pressurized under vacuum (reduced pressure; pressure 1 Pa or less) at a pressure of 1 MPa or less under the temperature conditions heated in step (b). The pressurization time is 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes.

[0082] [Step (d)] Step (d) is a step in which the substrate temperature is heated to a temperature of 130°C to 250°C while maintaining the pressure state of step (c). The holding time is 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes.

[0083] If the pre-bonding material of the present invention is used, and the laminate obtained through the above steps (a) to (d) is a laminate, then at least one of the first pre-bonding material layer and the second pre-bonding material layer has a minimum shear viscosity of 1 Pa·s to 10,000 Pa·s in the range of 130°C to 250°C. Therefore, the pre-bonding material can be well embedded in a substrate with a step difference. [Example]

[0084] Hereinafter, examples and comparative examples are shown to describe the present invention in more detail, but the present invention is not limited to these examples. Furthermore, in the following examples, parts are parts by weight. Also, Me represents methyl and Vi represents vinyl. The following shows compounds (M-1) to (M-5) used in the following examples of resin solution preparation.

[0085]

[0086] [Example 1: Preparation of Resin Solution] 24g of SEPTON 4033, a thermoplastic resin of hydrogenated styrene-isoprene-butadiene copolymer (containing 30% styrene, manufactured by KURARAY), was dissolved in 176g of isononane to obtain a 12% by mass isononane solution of hydrogenated styrene-isoprene-butadiene copolymer. The obtained solution was filtered through a 0.2μm membrane filter to obtain an isononane solution of thermoplastic resin (A-1).

[0087] [Example 2: Preparation of Resin Solution] 30g of SEPTON 4044, a thermoplastic resin of hydrogenated styrene-isoprene-butadiene copolymer (containing 32% styrene, manufactured by KURARAY), was dissolved in 176g of isononane to obtain a 12% by mass isononane solution of hydrogenated styrene-isoprene-butadiene copolymer. The obtained solution was filtered through a 0.2μm membrane filter to obtain an isononane solution of thermoplastic resin (A-2).

[0088] [Example 3 of resin solution preparation] In a flask equipped with a stirrer, thermometer, nitrogen purging device and reflux cooler, 43.1 g of 9,9'-bis(3-allyl-4-hydroxyphenyl)benzene (M-1), 29.5 g of an organohydrosiloxane with the average structural formula (M-3), 135 g of toluene, and 0.04 g of chloroplatinic acid were added, and the temperature was raised to 80°C. Then, 17.5 g of 1,4-bis(dimethylsilyl)benzene (M-5) was added dropwise to the flask over 1 hour. At this time, the temperature inside the flask rose to 85°C. After the dropwise addition was completed, the flask was matured at 80°C for 2 hours. Toluene was distilled off, and 80 g of cyclohexanone was added to obtain a resin solution with a resin solids concentration of 50% by mass and cyclohexanone as the solvent. When the molecular weight of the resin component in this solution was determined by GPC, the weight average molecular weight converted to polystyrene was 45,000. Furthermore, 7.5g of EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) as a crosslinking agent, 0.2g of BSDM (bis(tert-butylsulfonyl)diazomethane) manufactured by Wako Pure Chemical Industries, Ltd. as a curing catalyst, 0.1g of tetra[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (trade name: ADK STAB AO-60) as an antioxidant, and 0.1g of KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a release enhancer were added to 50g of this resin solution using a 1μm membrane filter to obtain resin solution (B-1). The elastic modulus of the (B-1) cured film, determined by dynamic viscoelasticity, was 300MPa at 25°C.

[0089] [Example 4 of resin solution preparation] In a 5L flask equipped with a stirrer, thermometer, nitrogen purging device and reflux cooler, 84.1g of epoxy compound (M-2) was dissolved in 600g of toluene, then 294.6g of compound (M-3) and 25.5g of compound (M-4) were added, and the mixture was heated to 60°C. Then, 1g of carbon-supported platinum catalyst (5% by mass) was added, and after confirming that the internal reaction temperature had risen to 65-67°C, it was further heated to 90°C and matured for 3 hours. Next, after cooling to room temperature, 600g of methyl isobutyl ketone (MIBK) was added, and the reaction solution was filtered under pressure to remove the platinum catalyst. The solvent in this resin solution was removed by vacuum distillation, and 270g of propylene glycol monomethyl ether acetate (PGMEA) was added to obtain a resin solution with a solid content concentration of 60% by mass using PGMEA as the solvent. When the molecular weight of the resin in this resin solution was determined by GPC, the weight-average molecular weight converted to polystyrene was 28,000. Furthermore, 9g of TEP-TPA (manufactured by Asahi Organics Co., Ltd.), a tetrafunctional phenol compound, 0.2g of tetrahydrophthalic anhydride (Rikacid HH-A, manufactured by Shin Nippon Rikka Co., Ltd.), and 0.1g of KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a release agent were added to 100g of this resin solution. The solution was filtered through a 1μm membrane filter to obtain resin solution (B-2). The elastic modulus of the (B-2) cured film, determined by dynamic viscoelasticity, was 500MPa at 25°C.

[0090] [Resin Solution Preparation Example 5] 100 parts of polydimethylsiloxane and 400 parts of isododecane were added to a solution consisting of 3 moles of vinyl groups at both ends and side chains, with SiMe2Vi groups blocking the molecular ends, and a number average molecular weight (Mn) of 50,000 as determined by GPC. The solution was then mixed with 5 parts of an organohydrogen polysiloxane as shown in formula (M-6). Furthermore, 0.05 parts of platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were added to the 100 parts of polydimethylsiloxane, and the solution was filtered through a 0.2 μm membrane filter to obtain a thermosetting silicate polymer solution (C-1).

[0091] [Resin Solution Preparation Example 6] 100 parts of polydimethylsiloxane and 400 parts of isododecane were added to a solution consisting of 3 moles of vinyl groups at both ends and side chains, with SiMe2Vi groups blocking the molecular ends, and a number average molecular weight (Mn) of 50,000 as determined by GPC. The solution was then mixed. Furthermore, 0.05 parts of platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were added to the 100 parts of polydimethylsiloxane, and the solution was filtered through a 0.2 μm membrane filter to obtain a thermosetting silica polymer solution (C-2).

[0092] [Example 1] After spin-coating the above-mentioned (C-1) solution onto a glass wafer with a diameter of 200 mm, a film corresponding to the (C) layer was formed by heating with a hot plate. Next, after spin-coating the above-mentioned (B-1) solution onto the (C) layer of the glass wafer on which the (C) layer was formed, a film corresponding to the (B) layer was formed by heating with a hot plate (step (a)). Table 1 shows the film formation sequence, heating conditions, and film thickness. Furthermore, the "amount of polymer containing siloxane bonds" in Table 1 refers to the mass parts of polymer containing siloxane bonds with a weight average molecular weight of 3,000 to 700,000 or less as measured by GPC, relative to 100 parts of the total mass of the pre-bonded material.

[0093] A silicon wafer with copper pillars of 200 mm diameter and 725 μm thickness, having copper pillars of 40 μm height and 40 μm diameter formed on its entire surface, is positioned opposite the surface of the glass wafer formed with the pre-adhesive layer in step (a). The wafer is preheated to 70°C in a bonding apparatus (step (b)). Next, in the bonding apparatus, the silicon wafer and the glass wafer are brought into contact under reduced pressure, and pressure is applied at 0.5 MPa (step (c)). Furthermore, while maintaining the pressure, the substrate temperature is heated to 180°C, and pressure is continued for 3 minutes after reaching 180°C (step (d)) to fabricate a laminate. The conditions for steps (b) to (d) are shown in Table 3.

[0094] [Examples 2-4 and Comparative Example 1] Examples 2-4 and Comparative Example 1 were treated in the same manner as Example 1 under the conditions described in Tables 1 and 3.

[0095] -Viscosity Measurement- Under the conditions of Example 1, the above-mentioned (C-1) solution was spin-coated onto a 200 mm diameter silicon wafer, and the material corresponding to layer (C) was formed by heating with a hot plate. On the other hand, the above-mentioned (B-1) solution was spin-coated onto a 200 mm diameter silicon wafer, and the material corresponding to layer (B) was formed by heating with a hot plate. Then, the respective pre-adhesive layers were peeled off from the silicon wafer to obtain two pre-adhesive films. The shear viscosity of each film was measured using HAAKE MARS manufactured by Thermo Fisher Scientific, according to the method described in JIS K 7244. The viscosity was measured within the range of 130 °C to 250 °C from room temperature at a heating rate of 10 °C / min. The lowest viscosity within this temperature range is recorded in the table. Furthermore, the measurement was performed at a wavenumber of 1 Hz and a spacing of 500 μm. Table 1 shows the lower of the minimum viscosities of the two pre-bonded films. Similarly, Examples 2-4 and Comparative Example 1 were measured in the same manner as in Example 1, and the results are shown in Table 1.

[0096] [Example 5] After spin-coating the above-mentioned (C-2) solution onto a glass wafer with a diameter of 200 mm, the material corresponding to layer (C) was formed by heating with a hot plate. On the other hand, after spin-coating the above-mentioned (B-1) solution onto the copper pillar surface of a silicon wafer with a diameter of 200 mm and a thickness of 725 μm and copper pillars with a height of 40 μm and a diameter of 40 μm formed all over the surface, the material corresponding to layer (B) was formed by heating with a hot plate (step (a)). The heating conditions and film thickness are shown in Table 2.

[0097] The silicon wafer with a pre-adhesive layer formed on its surface, which has copper pillars with a height of 40 μm and a diameter of 40 μm and a thickness of 200 mm and a thickness of 725 μm, fabricated in step (a), is aligned with the glass wafer with the pre-adhesive layer formed on its surface. It is preheated to 70°C in a bonding apparatus (step (b)). Next, in the bonding apparatus, the silicon wafer and the glass wafer are brought into contact under reduced pressure, and pressure is applied at 0.5 MPa (step (c)). Furthermore, while maintaining the pressure, the substrate temperature is heated to 180°C, and pressure is continued for 3 minutes after reaching 180°C (step (d)) to fabricate the laminate. Table 3 shows the conditions for steps (b) to (d).

[0098] [Examples 6-7 and Comparative Example 2] Under the conditions described in Tables 2 and 3, Examples 6-7 and Comparative Example 2 were also treated in the same way as Example 5.

[0099] -Viscosity Measurement- Under the conditions of Example 5, the above-mentioned (C-2) solution was spin-coated onto a 200 mm diameter silicon wafer, and then heated by a hot plate to form a film corresponding to the (C) layer. On the other hand, the above-mentioned (B-1) solution was spin-coated onto a 200 mm diameter silicon wafer, and then heated by a hot plate to form a film corresponding to the (B) layer. Then, the pre-adhesive layer was peeled off from the silicon wafer to obtain two pre-adhesive films. The viscosity of each film was measured in the range of 130°C to 250°C using the method described in JIS K 7244. Table 2 shows the lower of the minimum viscosities of the two pre-adhesive films. Similarly, Examples 6-7 and Comparative Examples 2 and 3 were measured in the same manner as in Example 5, and the results are shown in Table 2. Furthermore, the "amount of polymers containing siloxane bonds" in Tables 1 and 2 refers to the mass parts of polymers containing siloxane bonds with a weight average molecular weight of 3,000 to 700,000 as determined by GPC, relative to 100 parts of the total mass of the pre-bonded material.

[0100] Furthermore, in order to visually identify any abnormalities after the substrate is bonded, a glass plate is used as a support, but an opaque silicon substrate such as a wafer can also be used.

[0101] The following tests were performed on the bonded substrate (sample), and the results of the examples and comparative examples are shown in Table 4. Furthermore, the evaluations were carried out in the following order, but at the time point in the evaluation that was determined to be "×", the subsequent evaluations were terminated.

[0102] - Adhesion Test- After heating the laminate in an oven at 180°C for 1 hour, cool it to room temperature and visually confirm the adhesion of the interface. A good result is indicated by "○" if no abnormalities such as bubbles occur at the interface, and a poor result is indicated by "×".

[0103] -Backside Grinding Resistance Test- Using a grinding machine (DISCO DAG810), diamond grinding stones were used to heat-harden the resulting laminate (sample) in an oven at 180°C for 1 hour, as described above. The backside of the silicon wafer was then ground until the final substrate thickness reached 50 μm. After grinding, the wafer was inspected under an optical microscope (100x) for any abnormalities such as cracks or peeling. "○" indicates no abnormality, and "×" indicates an abnormality.

[0104] -CVD Durability Test- The processed material after back-side grinding of silicon wafers is introduced into a CVD apparatus to conduct a 2μm SiO2 film formation experiment and investigate whether there are any appearance abnormalities. "○" indicates no appearance abnormalities, and "×" indicates the occurrence of voids, wafer bulging, wafer damage, etc. The CVD durability test conditions are as follows. Apparatus name: Plasma CVD PD270STL (manufactured by SAMCO) RF500W, internal pressure 40Pa TEOS (tetraethyl orthosilicate): O2=20sccm: 680sccm

[0105] - Peelability Test- The peelability of the substrate is evaluated using the following method. First, on the wafer side of the wafer processed body that has completed the CVD durability test and is thinned to 50μm, a dicing tape is attached using a dicing frame. This dicing tape is then placed on the adsorption plate by vacuum adsorption. Then, at room temperature, one point of the glass is lifted with tweezers, and the glass substrate is peeled off. "○" indicates that the 50μm wafer can be peeled off without breaking. Abnormalities such as breaking are evaluated as unsatisfactory and are indicated by "×".

[0106]

[0107]

[0108]

[0109]

[0110] As shown in Table 4, in the pre-bonding materials that satisfy the requirements of the present invention, the pre-bonding of the substrate and the support is easy, and the peeling is also easy (Examples 1-7). On the other hand, in Comparative Examples 1-2 that do not satisfy the requirements of the present invention, there are problems with adhesion or peeling. In particular, although the shear viscosity of the pre-bonding material layer is within the range of the present invention, Comparative Example 2, in which the first pre-bonding material layer and the second pre-bonding material layer are not different, has poor peeling.

[0111] Furthermore, the present invention is not limited to the above-described embodiments. The above-described embodiments are illustrative, and any embodiment having a substantially the same structure as the technical concept described in the claims of the present invention and achieving the same effect is included within the technical scope of the present invention. [Simplified Explanation of the Diagram]

[0113] [Fig. 1] is a structural diagram showing an example of a laminate that uses the pre-adhesive material for substrate processing of the present invention to bond a substrate and a support.

Claims

1. A pre-adhesive material for substrate processing, used for pre-adheding a substrate to be processed on the back side to a support, characterized in that: relative to 100 parts by mass, the pre-adhesive material contains 10 to 100 parts by mass of a polymer containing siloxane bonds, with a weight average molecular weight of 3,000 to 700,000 as determined by GPC; the pre-adhesive material is composed of a two-layer structure having a first pre-adhesive layer and a second pre-adhesive layer with a different composition from the first pre-adhesive layer; wherein the polymer containing siloxane bonds contains the following: (p1) an organopolysiloxane having an alkenyl group in its molecule. (p2) An organohydrogen polysiloxane containing two or more hydrogen atoms bonded to silicon atoms (Si-H groups) in one molecule: the molar ratio of the Si-H groups in (p2) to the alkenyl groups in the aforementioned (p1) component is 0.3 to 15, and (p3) a platinum-based catalyst, wherein the minimum shear viscosity of any one or both of the aforementioned first pre-adhesive layer and the aforementioned second pre-adhesive layer is 1 Pa·s to 10,000 Pa·s in the range of 130°C to 250°C.

2. The pre-adhesive material for substrate processing as claimed in claim 1, wherein the aforementioned first pre-adhesive layer is composed of thermoplastic resin.

3. The pre-adhesive material for substrate processing as claimed in claim 1 or claim 2, wherein the aforementioned polymer containing siloxane bonds has repeating units as shown in the following general formula (1), [where R1 to R4 represent monovalent hydrocarbon groups with 1 to 8 carbon atoms that may be the same or different; m is an integer from 1 to 100, B is a positive number, and A is 0 or a positive number; however, A+B=1; X is a divalent organic group as shown in the following general formula (2); (where Z is a divalent organic group selected from any of them, N is 0 or 1; R5 and R6 are each alkyl or alkoxy groups with 1 to 4 carbon atoms that may be the same or different from each other; k is any one of 0, 1, or 2)].

4. The pre-adhesive material for substrate processing as claimed in claim 1 or claim 2, wherein the aforementioned polymer containing siloxane bonds is a repeating unit as shown in the following general formula (3), [where R7 to R10 represent monovalent hydrocarbon groups with 1 to 8 carbon atoms that may be the same or different; n is an integer from 1 to 100, D is a positive number, and C is 0 or a positive number; however, C+D=1; furthermore, Y is a divalent organic group as shown in the following general formula (4); (where V is a divalent organic group selected from any of them, p is 0 or 1; R11 and R12 are each alkyl or alkoxy groups with 1 to 4 carbon atoms that may be the same or different from each other; h is any one of 0, 1, or 2)].

5. A method for manufacturing a laminate, which is a method for manufacturing a laminate that bonds a substrate and a support through a pre-adhesive material, characterized by comprising the following steps (a) to (d): (a) forming a pre-adhesive layer on the bonding surface of either or both of the substrate and the support using a pre-adhesive material for substrate processing as described in any one of claims 1 to 5; (b) preheating either or both of the substrate and the support to a temperature of 30°C to 100°C; (c) bringing the substrate and the support into contact under reduced pressure through the pre-adhesive material and applying pressure at 1 MPa or less; (d) maintaining the pressure and heating the substrate temperature to a temperature of 130°C to 250°C.

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